CN100529193C - Jet electroform method and equipment for manufacturing foamed metal - Google Patents
Jet electroform method and equipment for manufacturing foamed metal Download PDFInfo
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- CN100529193C CN100529193C CNB200710024756XA CN200710024756A CN100529193C CN 100529193 C CN100529193 C CN 100529193C CN B200710024756X A CNB200710024756X A CN B200710024756XA CN 200710024756 A CN200710024756 A CN 200710024756A CN 100529193 C CN100529193 C CN 100529193C
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Abstract
This invention discloses method and apparatus for producing electroplated foam metal by spraying. The method comprises: placing surface-treated cathode plate into an electroforming tank, controlling the temperature of the electroforming solution at 20-65 deg.C, spraying via the spray nozzle connected with the central chamber of the anode bar to the cathode plate at a rate of 1.5-7.5 m/s to obtain a branch-like or sponge-like metal deposition layer, controlling the current density at 200-750 A/dm2, controlling the movement of the spray nozzle along the vertical direction, the horizontal lateral direction and horizontal longitudinal direction to form a porous foam metal deposition layer with required thickness and shape, and drying the foam metal deposition layer. The method has such advantages as no need for auxiliary medium, simple process and convenient production.
Description
Technical field
The present invention relates to a kind of process for preparing foam metal and equipment, especially a kind ofly need not to add manufacture method and the equipment that any assist medium can form foamed metal, specifically a kind of foamed metal jet electroform manufacture method and device thereof.
Background technology
As everyone knows, foamed metal is a kind of novel engineering materials, has three-dimensional reticulated structure, porosity height (40-98%, vol), specific surface area is big, in general, foam metal material has following characteristic: in light weight, permeability good, energy absorption is strong, thermal conductivity is low, electromagnetic wave shielding is good.Existing tens kinds of foamed metal preparation methods can be divided into following four classes substantially: liquid phase method, solid phase method, vapor phase process, electrodip process.The liquid phase method basic ideas are exactly before liquid metal solidification, are blown into, add means such as whipping agent or solid filler by adopting gas, form porous metal material.Liquid phase method is present most widely used class methods, and the technology of comparative maturity has gas insufflation, solid blowing agent method, lost wax process, seepage flow casting.The great advantage of liquid phase method is exactly to realize the production of mass-producing easily, but its a lot of shortcomings also make its application be very limited.The common thinking of these class methods is exactly to introduce the process of setting that a certain transition material removes to influence metal earlier, tries every possible means to remove this transition material then.This has just brought some inborn shortcomings, and such as the process control procedure complexity, homogeneity of structure is poor, and pore size is wayward, and the front and back aided process is many etc.The solid phase ratio juris is similar to liquid phase method, difference just in preparation process metal-powder keep solid-state, adopt sintering or other formed solid methods.These class methods also have the low shortcoming of intensity except some above-mentioned shortcomings of liquid phase method.Typical several solid phase method technologies are now: powder compacting method, slurry foaming, metal powder sintered method.Electrodip process is the effective means for preparing the good quality froth metal at present, and with the porosity height of the foamed metal of this method preparation, weave construction is even, and physics, mechanical property are good.Adopt this method can prepare multiple foam materialss such as nickel foam, copper, iron, aluminium, silver, lead.The basic step of this technology is at present: the required metal of porous plastics pre-treatment → electrochemical deposition → obtain foamed metal through aftertreatment (chemistry or thermal treatment).Foamed metal is non-conductive, and porous plastics is non-conductive, must conduct electricity pre-treatment before galvanic deposit, i.e. alligatoring, sensitization, activation, dispergation or reduction and electroless plating, and these main drawbacks of producing the method for foamed metals are: 1, equipment complexity; 2, technology is loaded down with trivial details; 3, the aperture is wayward.Therefore can utilize the galvanic deposit ultimate principle, improve manufacturing process, such as, can be on the conventional cathode body material, only change mass transfer mode and metal ion depositional mode in electric field of galvanic deposit electrolytic solution, prepare foamed metal fast, this new approaches with the directly quick manufacturing foamed metal of spontaneous rectangular formula that do not have other subsidiary material to get involved are to have very much feasibility.
Summary of the invention
The objective of the invention is all needs by means of the assist medium material at existing process for preparing foam metal, thereby cause complex process, porosity between the Kong Yukong is not high, the uppity problem in aperture is invented a kind of direct utilization and is sprayed method and the device thereof that principles of electro-deposition is made foamed metal.
Technical scheme of the present invention is:
A kind of foamed metal jet electroform manufacture method is characterized in that:
At first surface treated cathode plate is placed electrotyping bath;
Secondly, the temperature of electroforming solution is distinguished to some extent because of the kind difference of preparation metal, (wherein copper electroforming is at 20～30 ℃ between 20～65 ℃ for the temperature that generally is controlled at of electroforming solution, electroformed nickel is at 45～65 ℃), and make it to spray to cathode plate with the speed of 1.5～7.5m/s through the nozzle that links to each other with the center cavity of anode bar, obtain dendroid or spongy metal settled layer on the cathode plate surface, control anodic current density is at 200～750A/dm
2, control nozzle simultaneously and move longitudinally, so that form the foamed metal settled layer that porous desired thickness and shape, inner is communicated with on the cathode plate surface in vertical direction, horizontal cross and level; Metallographic phase in metal in this metal deposition layer and the electroforming solution in the main salt together;
At last, gained foamed metal settled layer being carried out drying treatment gets final product.
Described electroforming solution is to contain Cu, Ni, Fe, Al, Pb or they electroforming solution of alloy separately.。
In process for preparation, be added with anode activator and/or buffer reagent and/or brightening agent and/or wetting agent in the described electroforming solution, the addition of anode activator is 3～6% of an electroforming solution gross weight, the addition of buffer reagent is 2.5～5% of an electroforming solution gross weight, the addition of wetting agent is that the addition of 0.005～0.02% brightening agent of electroforming solution gross weight is 0.1～1% of an electroforming solution gross weight, and described anode activator is NiCl
2Deng, described buffer reagent is H
3BO
3, NH
4Cl etc., described wetting agent are that sodium lauryl sulphate, described brightening agent are asccharin, thiocarbamide, tonka bean camphor, 1,4-butynediol etc.
The pH value of control electroforming solution is between 3.0～4.2 in deposition process.
Described its shape of nozzle is circle, long strip shape or porous solid matter shape.
The manufacturing installation that of the present invention and aforesaid method adapts is as follows:
A kind of foamed metal jet electroform manufacturing installation, comprise reservoir 7, supply unit 2, pump 6, strainer 5, horizontal table 16, vertical lifting mechanism 17, temperature controller 8, well heater 9, in the electroforming solution in the temperature probe insertion reservoir 7 of temperature controller 8, the heating unit of well heater 9 also inserts in the electroforming solution in the reservoir 7, the output of temperature controller 8 links to each other with the control end of well heater 9, it is characterized in that cathode plate 14 is installed in the electrotyping bath 3, electrotyping bath 3 be installed in can be in the horizontal direction before and after and on the horizontal table 16 of move left and right, cathode plate 14 links to each other by the negative pole of lead with supply unit 2, is provided with the return line that the electroforming solution that makes the cathode plate 14 of flowing through flows back to reservoir 7 between electrotyping bath 3 and reservoir 7; Anode cavities 12 is installed above electrotyping bath 3, anode cavities 12 is installed on the bearing 18, bearing 18 is installed in and drives on its vertical lifting mechanism that moves up and down 17, anode cavities 12 moves up and down under the drive of bearing 18, anode bar 13 is installed in the anode cavities 12, anode bar 13 is provided with centre hole 19, the lower end of this centre hole 19 communicates with nozzle 11, it is outer relative with cathode plate 14 that the exit end of nozzle 11 stretches out anode cavities 12, the upper end of anode bar 13 links to each other by the output terminal of connecting tube with strainer 5, the input terminus of strainer 5 links to each other with the output terminal of pump 6, and the input terminus of pump 6 links to each other with reservoir 7, and anode bar 13 links to each other by the positive pole of lead with supply unit 2.
On the pipeline that connects strainer 5 and anode bar 13 centre holes 19 upper ends, be installed under meter 15 and tensimeter 1, be connected to surplus valve 4 by between the exit end of strainer 5 and reservoir 7.
Described horizontal table 16 all links to each other with computer control system 10 with vertical lifting mechanism 17.
Beneficial effect of the present invention:
The present invention has changed existing production method and technology fully, under normal temperature, normal pressure, adopt the relevant principle of electrochemical method, in conjunction with basic technology characteristics and the working method and the foamed metal technology of preparing of spraying galvanic deposit, propose a kind of novel forming method that can directly make foamed metal-foamed metal and sprayed electrodip process, even with the foamed metal thickness that the inventive method is made, do not crack or rupture the porosity height; Pore diameter range is big.Electric deposition device is easy and simple to handle in addition, takes up an area of few.The characteristics of method of the present invention are: 1, electroforming solution sprays to cathode interface at a high speed from anode cavities at a high speed under the certain pressure effect, has changed the mass transfer process of metal ion fully.Compare with the regular troughs casting, can reduce the metal diffusing layer thickness greatly towards liquid at a high speed, accelerate the velocity of diffusion of metal ion, improved the limit current density of electrodeposition process.Adopt bigger current density, the also corresponding quickening of sedimentation velocity, concentration polarization aggravation, thereby cause lacking enough metal ions at the cathode interface place and generation tree is dendritic or the spongy metal settled layer, microscopic analysis shows that the metal deposition layer tissue is loose, be loose and porous structure, the porosity height.In addition, because extension, the butt joint effect of dendritic crystal, metal deposition layer is porous and is communicated with phenomenon.2, spraying electrodeposition technology can carry out galvanic deposit with the cathode current density far above the common electrical depositing operation, therefore can be implemented in the high speed electro-deposition on the cathode surface unit surface.3, anode nozzle has multiple shapes such as circle (bore is 0.1-1mm), long strip shape and porous solid matter to satisfy the requirement of different situations; In addition under computer control, can realize the relative movement of nozzle laterally (X to) and vertical (Y to) three directions in vertical direction (Z to) and horizontal direction.4, spray the galvanic deposit utilization under high cathode current density, can independently generate dendroid or this characteristic of spongy metal settled layer is carried out the manufacturing work of foamed metal, therefore compare with other foamed metal manufacturing process, do not have in the manufacturing processed other subsidiary material (such as, solid foamed Ji, organic plastics etc.) intervention.5, the foamed metal thickness that adopts electrodeposition technology to make is even, does not crack or ruptures, and the foamed metal quality of production is good.Because vertical injection galvanic deposit mode, in the working process anode and negative electrode over against, the two-stage spacing changes hardly. thereby even at the sedimentary metal in foamed metal two sides.6, electric deposition device processing ease, occupation of land are lacked.Machine tool main body is a vertical structure, and anode bar is the vertical anode cavities that is installed in, and the top of anode cavities is opened wide, and does not have obstacle, thereby adds, changes anode bar, and operations such as adjustment two-stage spacing all are very easy to carry out bring convenience to operation, increase work efficiency.In addition, the vertical machine floor space is little, saves initial cost.So successful Application of the present invention will be significant to the development and the Application Areas of spraying electro-deposition techniques and foamed metal manufacturing process.
Utilize metal grain short texture, the porous of the metal deposition layer of gained of the present invention, crystallization mode is dendroid.Utilize the nickel foam of its preparation to use and make multiple electrochemistry in industry reaction electrode and fuel cell electrode, can be used to purifying motor tail gas and industrial gaseous waste, waste water as catalyst carrier, also can be used as the device of filtration, heating, heat exchange, damping, noise elimination etc.
Manufacturing installation of the present invention has cheap, the characteristics such as realization that are easy to simple in structure, and it is even that it can prepare foamed metal thickness, do not crack or rupture porosity height, the foamed metal of size range between hundreds of nanometer and micron up to a hundred; In addition, can also select different metallic substance and electric depositing solution prescription according to the practical use of foamed metal, the scope of shaped material is wide.
Integrated use of the present invention the relevant principle of electrochemistry, spray the galvanic deposit utilization under high cathode current density, can independently generate dendroid or this characteristic of spongy metal settled layer is carried out the manufacturing work of foamed metal, therefore compare with other foamed metal manufacturing process, do not have in the manufacturing processed other subsidiary material (such as, solid foamed Ji, organic plastics etc.) intervention.
The present invention is that the Application Areas of widening foamed metal provides the foundation.
Description of drawings
Fig. 1 is the structural representation of manufacturing installation of the present invention.
Fig. 2 is an anode unit hoisting appliance synoptic diagram of the present invention.
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples.
A kind of foamed metal jet electroform manufacture method, it may further comprise the steps:
At first surface treated cathode plate is placed electrotyping bath;
Secondly, the temperature of electroforming solution is distinguished to some extent because of the kind difference of preparation metal, electroforming solution generally be controlled at temperature between 20～65 ℃, (wherein copper electroforming is at 20～30 ℃, electroformed nickel is at 45～65 ℃) and make it to spray to cathode plate through the nozzle that links to each other with the center cavity of anode bar with the speed of 1.5～7.5m/s, obtain dendroid or spongy metal settled layer on the cathode plate surface, control current density is at 200～750A/dm
2, control nozzle simultaneously and move longitudinally, so that form the foamed metal settled layer that porous desired thickness and shape, inner is communicated with on the cathode plate surface in vertical direction, horizontal cross and level;
At last, gained foamed metal settled layer being carried out drying treatment gets final product.
Ultimate principle of the present invention is: according to the practical use of foamed metal, select different metallic substance and electric depositing solution prescription, the mode that adopts electroforming solution to spray then sprays to negative electrode at a high speed from the sun level, on cathode plate surface by electric deposition nickel, acid copper or other different metals, usually under bigger current density (as current density between 120～1000A/dm
2The time), stratiform, the massive transformation of the form of electrocrystallization during by low current density is dendroid.The crystallizing layer of this dendritic structure is thickeied gradually, is extended, and has finally formed loose, porous foamy structure gradually, and wherein the shape of foamed metal and thickness are controlled by control shaping track and depositing time.For loose, the porous that can realize the foamed metal settled layer is the dendritic structure of principal feature, improve the porosity of foamed metal, guarantee to be interconnected, to increase surface-area between the space.Also should consider forming technology parameter (such as, the speed that cathode current density, track move, the distance of injection and speed) to the influence of foamed metal microtexture and macro property.Concerning the galvanic deposit of porous material, should obtain uniform settled layer as far as possible, to guarantee the consistence of foamed metal performance.Yet in actual fabrication process, owing to be subjected to the influence of electrochemistry and several how factors, it is uneven that electric current distributes at cathode surface, and thickness of coating can be uneven yet, therefore in order further to improve the deposition quality of foamed metal.In preparation process, the casting liquid in except that main salt, also to increase anode activator and/or buffer reagent and/or brightening agent and/or wetting agent, the addition of anode activator is 3～6% of an electroforming solution gross weight, the addition of buffer reagent is 2.5～5% of an electroforming solution gross weight, the addition of wetting agent is that the addition of 0.005～0.02% brightening agent of electroforming solution gross weight is 0.1～1% of an electroforming solution gross weight, and described anode activator is NiCl
2, described buffer reagent is H
3BO
3, NH
4Cl, described wetting agent are sodium lauryl sulphate, and described brightening agent is asccharin, thiocarbamide, tonka bean camphor, 1, the 4-butynediol.
In electrodeposition process, current density is controlled at (can be at 120～1000A/dm in certain scope
2Between) select; Be shaped the discovery current density at 200～750A/dm according to reality
2Form loose porous pine-tree structure easily, also should strictly control the pH value between 3.0～4.2, the pH value is lower than at 3.0 o'clock, separates out hydrogen on the negative electrode in a large number, and current efficiency is low; The pH value is higher than at 4.2 o'clock, and deposited phenomenon can take place metal ion in the electroforming solution.Temperature is also influential to internal stress, dispersive ability, the plating speed of coating in the electrodeposition process, so should regulate by corresponding temperature controller and well heater, the temperature of electroforming solution is controlled between 20～65 ℃.Make electroforming solution keep recurrent state in the reservoir by the electroforming solution in the electrotyping bath being drawn get back in the electrodeposition process, its role is to make intrapore electroforming solution in time to obtain upgrading, keep the homogeneity of settled layer, by strong convection current, diffusion, quicken the transmission course of plating bath, also help the effusion of hydrogen simultaneously.
During concrete enforcement, the present invention also can further be decomposed into following steps:
1, the surface treatment of cathode plate.Comprise that the anticathode pole plate polishes successively, oil removing, passivation, washing, drying treatment.Wherein polishing can adopt 1, mechanical polishing, 2, electropolishing, 3, chemical rightenning, its objective is the zone of oxidation of thoroughly removing polar board surface, be difficult for removing stain and small burr.According to size and shape need, can select one or several methods of above-mentioned finishing method.Clean mandrel surface repeatedly with acetone or dehydrated alcohol,, then pole plate is placed dilute sulphuric acid etch for some time, repeatedly wash after drying with distilled water at last so that it is carried out oil removal treatment.
2, metal electrodeposition is shaped.Its working process is to make pressurization and the filtration of the electroforming solution of process heating, temperature control through magnetic drive pump and strainer, spray to the cathode plate surface that is fixed in the galvanic deposition cell through hand line nozzle at a high speed with the form of spraying, the electroforming solution of the cathode plate of flowing through is at last got back in the reservoir through return line.Behind the power connection, metal anode dissolves in anode cavities, and metal ion is deposited on the cathode plate, forms the electrodeposit metals layer.Whole process is carried out computer control, computer control system can be according to the horicontal motion mechanism and the vertical movement mechanism of the worktable of the actual three-dimensional dimension control step electrode drive lathe of contoured foam metal, make nozzle and negative electrode produce X, Y, Z to relative movement, realize the scanning on nozzle anticathode surface.
Should adopt the deionized-distilled water preparation on the electroforming solution, entering of pollutent or impurity avoided in strictness in the layoutprocedure, after preparation finishes, needs to carry out the removal of impurity to electroforming solution and handles.
In the present embodiment, the metal material that is suitable for making foamed metal comprises Cu, Ni, Fe, Al, Pb and alloy thereof etc.
3, metal aftertreatment.Its operation for foamed metal purify successively, drying treatment.Steps such as chemical reagent cleaning, ultra-sonic oscillation purification, clear water circulation flushing can be successively adopted in purification, its objective is and thoroughly remove electroforming solution and other impurity that enters the metal space and remain in the metallic surface.Then metal products is placed on and carries out drying treatment in the drying machine, look drying machine type and product size time of drying and determine.Drying temperature is generally 100-300 ℃.Time of drying is generally about 3 hours.
Below be several examples that utilize aforesaid method to make foamed metal, give an actual example that those skilled in the art can specifically implement the present invention according to the prompting of the embodiment of the invention in the aforementioned parameters scope but be not limited only to following institute.
Embodiment 1:
Select for use stainless steel (1Cr18Ni9Ti) as cathode plate, polar board surface is carried out successively, polishing, oil removing, passivation, washing, drying treatment adopt the injection electrodeposition technology to arrive expection thickness at its surperficial uniform deposition then.
Electroforming solution preparation formula (is example to prepare 1000 electroforming solution that restrain):
Copper sulfate 250 grams, sulfuric acid 50 grams, asccharin 1 gram (brightening agent), surplus 699 grams are deionized-distilled water.
The metal electrodeposition forming technology:
Nozzle form is a long strip shape, and specification is 1 * 20mm (looking particular case), electroforming solution jet velocity v=7.5m/s, and cathode current density is J=250A/dm
2The pH value of control electroforming solution is 4 in the deposition process, electroforming solution temperature T=25 ℃, curring time t=4h (deciding according to shape need)
Post-processing step:
Drying temperature T=200 ℃, time of drying t=2h.
Select for use stainless steel (1Cr18Ni9Ti) as cathode plate, polar board surface is carried out successively, polishing, oil removing, passivation, washing, drying treatment adopt the injection electrodeposition technology to arrive expection thickness at its surperficial uniform deposition then.
Electroforming solution preparation formula (is example to prepare 1000 electroforming solution that restrain):
Copper sulfate 250 grams, sulfuric acid 55 grams, asccharin (brightening agent) 1 gram, sodium lauryl sulphate (wetting agent) 0.05 gram, surplus is deionized-distilled water 693.95 grams.
The metal electrodeposition forming technology:
Nozzle form is a long strip shape, and specification is 1 * 20mm (looking particular case), electroforming solution jet velocity v=1.5m/s, and cathode current density is J=200A/dm
2The pH value of control electroforming solution is 3 in the deposition process, electroforming solution temperature T=20 ℃, curring time t=4h (shape need and decide).
Post-processing step:
Drying temperature T=200 ℃, time of drying t=2h.
Select for use stainless steel (1Cr18Ni9Ti) as cathode plate, polar board surface is carried out successively, polishing, oil removing, passivation, washing, drying treatment adopt the injection electrodeposition technology to arrive expection thickness at its surperficial uniform deposition then.
Electroforming solution preparation formula (is example to prepare 1000 electroforming solution that restrain):
Copper sulfate 250 grams, sulfuric acid 60 grams, thiocarbamide (brightening agent) 10 grams, NH
4Cl (buffer reagent) 40 grams, sodium lauryl sulphate (wetting agent) 0.2 gram, surplus is the deionized-distilled water of 639.8 grams.
The metal electrodeposition forming technology:
Nozzle form is a long strip shape, and specification is 1 * 20mm (looking particular case), electroforming solution jet velocity v=7.5m/s, and cathode current density is J=750A/dm
2The pH value of control electroforming solution is 4.2 in the deposition process, electroforming solution temperature T=30 ℃, curring time t=4h (deciding according to shape need).
Post-processing step:
Drying temperature T=200 ℃, time of drying t=2h.
Select for use stainless steel (1Cr18Ni9Ti) as cathode plate, to polar board surface polish successively, oil removing, passivation, washing, drying treatment, adopt then spray electrodeposition technology at its surperficial uniform deposition to expection thickness.
Electroforming solution configuration prescription (is example to prepare 1000 electroforming solution that restrain):
Single nickel salt 250 grams, nickelous chloride (anode activator) 35 grams, boric acid (buffer reagent) 30 grams, sodium lauryl sulphate (wetting agent) 0.1 gram, asccharin (brightening agent) 1 gram, deionized-distilled water 683.9 grams;
The metal electrodeposition forming technology:
Nozzle form is a long strip shape, and specification is 1 * 20mm (with an example 1), electroforming solution jet velocity v=1.5m/s, and cathode current density is J=200A/dm
2The pH value of control electroforming solution is 4 in the deposition process, electroforming solution temperature T=40 ℃, curring time t=4h;
Post-processing step:
Drying temperature T=200 ℃, time of drying t=2h.
The selecting for use and handling of cathode plate with example 1
Electroforming solution configuration prescription (is example to prepare 1000 electroforming solution that restrain):
Single nickel salt 250 grams, nickelous chloride (anode activator) 30 grams, boric acid (buffer reagent) 20 grams, sodium lauryl sulphate (wetting agent) 0.05 gram, thiocarbamide (brightening agent) 1 gram, deionized-distilled water 698.95 grams;
The metal electrodeposition forming technology:
Nozzle form is a long strip shape, and specification is 1 * 20mm (with an example 1), electroforming solution jet velocity v=1.5m/s, and cathode current density is J=200A/dm
2Electroforming solution temperature T=45 ℃, the pH value of control electroforming solution is 3 in the deposition process, curring time t=4h;
Post-processing step:
Drying temperature T=200 ℃, time of drying t=2h.
The selecting for use and handling of cathode plate with example 1
Electroforming solution configuration prescription (is example to prepare 1000 electroforming solution that restrain):
Single nickel salt 250 grams, nickelous chloride (anode activator) 60 grams, boric acid (or NH
4The Cl buffer reagent) 50 grams, sodium lauryl sulphate (wetting agent) 0.2 gram, tonka bean camphor and 1,4-butynediol (brightening agent) are totally 10 grams, deionized-distilled water 629.8 grams;
The metal electrodeposition forming technology:
Nozzle form is a long strip shape, and specification is 1 * 20mm (with an example 1), electroforming solution jet velocity v=7.5m/s, and cathode current density is J=750A/dm
2Electroforming solution temperature T=65 ℃, the pH value of control electroforming solution is 4.2 in the deposition process, curring time t=4h;
Post-processing step:
Drying temperature T=200 ℃, time of drying t=2h.
Copper and mickel among the embodiment 1～6 replaces just having constituted new embodiment of the present invention with Fe, Al, Pb respectively.
Manufacturing installation of the present invention as shown in Figure 1, 2.
Among the figure: 1 is tensimeter, and 2 is supply unit, and 3 is that electrotyping bath, 4 is surplus valve, 5 is strainer, and 6 is magnetic drive pump, and 7 is that reservoir, 8 is temperature controller, 9 is well heater, 10 is computer control system, and 11 is anode nozzle, and 12 is anode cavities, 13 is anode bar, 14 is cathode plate, and 15 is under meter, and 16 is that X-Y worktable, 17 is that Z axle vertical mechanism, 18 is that bearing, 19 is the anodes centre hole.
A kind of foamed metal jet electroform manufacturing installation, comprise reservoir 7, supply unit 2, pump 6 (can adopt magnetic drive pump when specifically implementing), strainer 5, horizontal table 16, vertical lifting mechanism 17, (model is temperature controller 8: PT100), well heater 9 etc., as shown in Figure 1, in the electroforming solution in the temperature probe insertion reservoir 7 of temperature controller 8, the heating unit of well heater 9 also inserts in the electroforming solution in the reservoir 7, the output of temperature controller 8 links to each other with the control end of well heater 9, cathode plate 14 is installed in the electrotyping bath 3, electrotyping bath 3 be installed in can be in the horizontal direction before and after and on the horizontal table 16 of move left and right, cathode plate 14 links to each other by the negative pole of lead with supply unit 2, is provided with the return line that the electroforming solution that makes the cathode plate 14 of flowing through flows back to reservoir 7 between electrotyping bath 3 and reservoir 7; Anode cavities 12 is installed above electrotyping bath 3, anode cavities 12 is installed on the bearing 18, bearing 18 is installed in and drives on its vertical lifting mechanism that moves up and down 17, anode cavities 12 under the drive of bearing 18, move up and down (as Fig. 2), anode bar 13 is installed in the anode cavities 12, anode bar 13 is provided with centre hole 19, the lower end of this centre hole 19 communicates with nozzle 11, it is outer relative with cathode plate 14 that the exit end of nozzle 11 stretches out anode cavities 12, the upper end of anode bar 13 links to each other by the output terminal of connecting tube with strainer 5, the input terminus of strainer 5 links to each other with the output terminal of pump 6, the input terminus of pump 6 links to each other with reservoir 7, and anode bar 13 links to each other by the positive pole of lead with supply unit 2.On the pipeline that connects strainer 5 and anode bar 13 centre holes 19 upper ends, be installed under meter 15 and tensimeter 1, be connected to surplus valve 4 by between the exit end of strainer 5 and reservoir 7.Horizontal table 16 wherein and vertical lifting mechanism 17 can adopt numerical control device of the prior art to be realized, make the orbiting motion of their follow procedure settings under the control of computer control system 10, to obtain the foamed metal settled layer of satisfied shape and thickness.
The prior aries that maybe can adopt all same as the prior art such as the well heater 9 that does not describe in detail in the present embodiment, magnetic drive pump 6, supply unit 2, strainer 5, computer control system 10 are realized.
This manufacturing installation adopts conductive core (as stainless steel etc.) to make cathode material, before electroforming, need to core polish, polish, pre-treatment such as cleaning.Adopt insulating material to make anode cavities, adopt highly purified metal bar to be processed into anode bar, electroforming solution circulating filtration 4～7 times, and by 8,9 pairs of electroforming solution heating of heating temperature control device, insulation.Its working process is pressurization and the filtration of the electroforming solution of process heating, temperature control through magnetic drive pump and strainer, at a high speed spray to the cathode surface that be fixed in electrotyping bath through nozzle with the form of spraying through osculum, the electroforming solution of the negative electrode of flowing through is at last got back in the reservoir through return line.After direct supply was connected, anode bar began dissolving, and the metal ion deposition forms the electroforming metal layer on cathode plate.Whole process is carried out computer control, computer control system can be according to the X-Y worktable and the Z axle vertical mechanism of the actual three-dimensional dimension control step electric motor driving lathe of contoured foam metal, make nozzle and negative electrode produce X, Y, Z to relative movement, realize the scanning on nozzle anticathode surface.Adopt aforesaid method, accelerate the mass transfer velocity of metal ion, reduced the ion diffusion layer thickness in cathodic deposition zone, increased substantially cathode current density, so just change the crystallization mode of metal ion, helped forming the high foam metal material of porosity.
Claims (5)
1, a kind of foamed metal jet electroform manufacture method is characterized in that:
At first surface treated cathode plate is placed electrotyping bath;
Secondly, control the temperature of electroforming solution between 20～65 ℃ according to the difference of the kind for preparing metal, and make described electroforming solution spray to cathode plate with the speed of 1.5～7.5m/s through the nozzle that links to each other with the center cavity of anode bar, obtain dendroid or spongy metal settled layer on the cathode plate surface, control anodic current density is at 200～750A/dm
2, control nozzle simultaneously and move longitudinally, so that form the foamed metal settled layer that porous desired thickness and shape, inner is communicated with on the cathode plate surface in vertical direction, horizontal cross and level;
At last, gained foamed metal settled layer being carried out drying treatment gets final product.
2, foamed metal jet electroform manufacture method according to claim 1, it is characterized in that: described electroforming solution is the electroforming solution that contains Cu, Ni, Fe, Al or Pb.
3, foamed metal jet electroform manufacture method according to claim 1 and 2 is characterized in that: described electroforming solution is added with a kind of in anode activator, buffer reagent, brightening agent and the wetting agent at least in process for preparation; The addition of described anode activator is 3～6% of an electroforming solution gross weight, the addition of buffer reagent is 2～5% of an electroforming solution gross weight, the addition of wetting agent is 0.005～0.02% of an electroforming solution gross weight, and the addition of brightening agent is 0.1～1% of an electroforming solution gross weight; Described anode activator is NiCl
2, described buffer reagent is H
3BO
3Or NH
4Cl, described wetting agent are sodium lauryl sulphate, and described brightening agent is asccharin, thiocarbamide, tonka bean camphor or 1, the 4-butynediol.
4, foamed metal jet electroform manufacture method according to claim 1 is characterized in that: the pH value of control electroforming solution is between 3.0～4.2 in deposition process.
5, foamed metal jet electroform manufacture method according to claim 1 is characterized in that described its shape of nozzle is circle, long strip shape or porous solid matter shape.
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| CN101994137B (en) * | 2010-12-15 | 2012-02-08 | 南京航空航天大学 | Method and device for processing revolving parts by high-speed jet injection and electroforming |
| CN102212848A (en) * | 2011-05-09 | 2011-10-12 | 淮海工学院 | Device and method for preparing foam metal by virtue of cross electrodeposition |
| CN103255452B (en) * | 2013-05-03 | 2016-02-24 | 中国人民解放军装甲兵工程学院 | A kind of selective metal electric deposition device and application thereof |
| CN103290446B (en) * | 2013-06-18 | 2015-08-19 | 长沙岱勒新材料科技股份有限公司 | Diamond surface electroplating device and electro-plating method |
| CN103481672B (en) * | 2013-09-30 | 2016-06-22 | 陈泽进 | 3D printer is piled up in electrolytic etching plating |
| CN107385480A (en) * | 2017-08-05 | 2017-11-24 | 江苏省海洋资源开发研究院(连云港) | A kind of device and process for preparing metal base ultra-hydrophobicity surface |
| CN108914177A (en) * | 2018-08-03 | 2018-11-30 | 南京航空航天大学 | A kind of device and method of the fine liquid line metal 3D printing of five axis |
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| CN115337879B (en) * | 2021-05-14 | 2024-04-16 | 中国科学院理化技术研究所 | Liquid metal hollow microsphere and preparation method and application thereof |
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